Ink jet recording element

ABSTRACT

The present invention relates to an ink jet recording element having very good dye keeping properties in time. Said ink jet recording element comprises a support and at least one ink-receiving layer, said ink-receiving layer comprising at least one hydrosoluble binder and at least one aluminosilicate polymer obtainable by a preparation method consisting in treating an aluminum halide with an alkyl orthosilicate only having hydrolyzable functions with an aqueous alkali in the presence of silanol groups, the aluminum concentration being maintained less than 0.3 mol/l, the Al/Si molar ratio being maintained between 1 and 3.6 and the alkali/Al molar ratio being maintained between 2.3 and 3; and then stirring the resulting mixture at ambient temperature in the presence of silanol groups for long enough to form the aluminosilicate polymer.

FIELD OF THE INVENTION

The present invention relates to an ink jet recording element.

DESCRIPTION RELATIVE TO THE PRIOR ART

Digital photography has been growing fast for several years; the generalpublic now having access to efficient and reasonably priced digitalcameras. Therefore people are seeking to be able to produce photographicprints from a simple computer and its printer, with the best possiblequality.

Many printers, especially those linked to personal office automation,use the inkjet printing technique. There are two major families ofinkjet printing techniques: continuous jet and drop-on-demand.

Continuous jet is the simpler system. Pressurized ink (3.10⁵ Pa) isforced to go through one or more nozzles so that the ink is transformedinto a flow of droplets. In order to obtain the most regular possiblesizes and spaces between drops, regular pressure pulses are sent usingfor example a piezoelectric crystal in contact with the ink with highfrequency (up to 1 MHz) alternating current (AC) power supply. So that amessage can be printed using a single nozzle, every drop must beindividually controlled and directed. Electrostatic energy is used forthis: an electrode is placed around the ink jet at the place where dropsform. The jet is charged by induction and every drop henceforth carriesa charge whose value depends on the applied voltage. The drops then passbetween two deflecting plates charged with the opposite sign and thenfollow a given direction, the amplitude of the movement beingproportional to the charge carried by each of the plates. To preventother drops from reaching the paper, they are left uncharged: so,instead of going to the support they continue their path without beingdeflected and go directly into a container. The ink is then filtered andcan be reused.

The other category of inkjet printer is drop-on-demand (DOD). Thisconstitutes the base of inkjet printers used in office automation. Withthis method, the pressure in the ink cartridge is not maintainedconstant but is applied when a character has to be formed. In onewidespread system there is a row of 12 open nozzles, each of them beingactivated with a piezoelectric crystal. The ink contained in the head isgiven a pulse: the piezo element contracts with an electric voltage,which causes a decrease of volume, leading to the expulsion of the dropby the nozzle. When the element resumes its initial shape, it pumps inthe reservoir the ink necessary for new printings. The row of nozzles isthus used to generate a column matrix, so that no deflection of the dropis necessary. One variation of this system consists in replacing thepiezoelectric crystals by small heating elements behind each nozzle. Thedrops are ejected following the forming of bubbles of solvent vapor. Thevolume increase enables the expulsion of the drop. Finally, there is apulsed inkjet system in which the ink is solid at ambient temperature.The print head thus has to be heated so that the ink liquefies and canprint. This enables rapid drying on a wider range of products thanconventional systems.

There now exist new “inkjet” printers capable of producing photographicimages of excellent quality. However, they cannot supply good proofs ifinferior quality printing paper is used. The choice of printing paper isfundamental for the quality of obtained image. The printing paper mustcombine the following properties: high quality printed image, rapiddrying after printing, good dye keeping in time, smooth appearance andhigh gloss.

In general, the printing paper comprises a support coated with one ormore layers according to the properties required. It is possible, forexample, to apply on a support a primary attachment layer, an absorbentlayer, an ink fixing layer and a protective layer or surface layer toprovide the glossiness of the recording element. The absorbent layerabsorbs the liquid part of the water-based ink composition aftercreation of the image. Elimination of the liquid reduces the risk of inkmigration to the surface. The ink fixing layer prevents any ink lossinto the fibers of the paper base to obtain good color saturation whilepreventing excess ink that would encourage the increase in size of theprinting dots and reduce the image quality. The absorbent layer andfixing layer can also constitute a single ink-receiving layer ensuingboth functions. The protective layer is designed to ensure protectionagainst fingerprints and the pressure marks of the printer feed rollers.The ink-receiving layer usually comprises a binder, a receiving agentand various additives. The purpose of the receiving agent is to fix thedyes in the printing paper. The best-known inorganic receivers arecolloidal silica or boehmite. For example, the European PatentApplications EP-A-976,571 and EP-A-1,162,076 describe materials forinkjet printing in which the ink-receiving layer contains as inorganicreceivers Ludox™ CL (colloidal silica) marketed by Grace Corporation orDispal™ (colloidal boehmite) marketed by Sasol. However, printing papercomprising an ink-receiving layer containing such inorganic receiverscan have poor image stability in time, which is demonstrated by a lossof color density.

To meet the new requirements of the market in terms of photographicquality, printing speed and color stability, it is necessary to offer anew ink jet recording element having the properties as defined above,more particularly good dye keeping in time as well as a high gloss.

SUMMARY OF THE INVENTION

The new ink jet recording element according to the present inventioncomprises a support and at least one ink-receiving layer, and ischaracterized in that said ink-receiving layer comprises at least onehydrosoluble binder and at least one aluminosilicate polymer obtainableby a preparation method that comprises the following steps:

a) treating a mixed aluminum and silicon alkoxide only comprisinghydrolyzable functions, or a mixed aluminum and silicon precursorresulting from the hydrolysis of a mixture of aluminum compounds andsilicon compounds only comprising hydrolyzable functions, with anaqueous alkali, in the presence of silanol groups, the aluminumconcentration being maintained at less than 0.3 mol/l, the Al/Si molarratio being maintained between 1 and 3.6 and the alkali/Al molar ratiobeing maintained between 2.3 and 3;

b) stirring the mixture resulting from step a) at ambient temperature inthe presence of silanol groups long enough to form the aluminosilicatepolymer; and

c) eliminating the byproducts formed during steps a) and b) from thereaction medium.

Throughout the present description, the expression “hydrolyzablefunction” means a substituent eliminated by hydrolysis during theprocess and in particular at the time of treatment with the aqueousalkali. In the following, the expression “unmodified mixed aluminum andsilicon alkoxide” or “unmodified mixed aluminum and silicon precursor”means respectively a mixed aluminum and silicon alkoxide only havinghydrolyzable functions, or a mixed aluminum and silicon precursorresulting from the hydrolysis of a mixture of aluminum compounds andsilicon compounds only having hydrolyzable functions. More generally, an“unmodified” compound is a compound that only comprises hydrolyzablesubstituents.

The ink jet recording element according to the present invention hasimproved dye keeping properties in time as well as a good gloss comparedwith the ink jet recording elements available on the market.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 to 3 represent the spectra obtained by Raman spectroscopy of thealuminosilicate polymers used for comparative purposes and used in thepresent invention.

FIGS. 4 to 19 represent the percentage of color density loss for variouscomparative recording elements and according to the present inventionwhen exposed to ozone.

DETAILED DESCRIPTION OF THE INVENTION

The ink jet recording element according to the present inventioncomprises firstly a support. This support is selected according to thedesired use. It can be a transparent or opaque thermoplastic film; inparticular a film based on polyester, polymethylmetacrylate, celluloseacetate, or polyvinyl chloride, and any other appropriate material. Thesupport used in the invention can also be paper, both sides of which maybe covered with a polyethylene layer. When the support comprising thepaper pulp is coated on both sides with polyethylene, it is called ResinCoated Paper (RC Paper) and is marketed under various brand names. Thistype of support is especially preferred to constitute a inkjet recordingelement. The side of the support that is used can be coated with a verythin layer of gelatin or another composition to ensure the adhesion ofthe first layer on the support.

The ink jet recording element according to the invention then comprisesat least one ink-receiving layer comprising at least one hydrosolublebinder. Said hydrosoluble binder can be gelatin or polyvinyl alcohol.The gelatin is that conventionally used in the photographic field. Sucha gelatin is described in Research Disclosure, September 1994, No.36544, part IIA. Research Disclosure is a publication of Kenneth MasonPublications Ltd., Dudley House, 12 North Street, Emsworth, HampshirePO10 7DQ, United Kingdom. The gelatin can be obtained from SKW and thepolyvinyl alcohol from Nippon Gohsei, or Air Product under the nameAirvol® 130.

According to the present invention, the ink-receiving layer comprises,as receiving agent, at least one aluminosilicate polymer obtainable by apreparation method comprising the following steps:

a) treating a mixed aluminum and silicon alkoxide only comprisinghydrolyzable functions, or a mixed aluminum and silicon precursorresulting from the hydrolysis of a mixture of aluminum compounds andsilicon compounds only comprising hydrolyzable functions, with anaqueous alkali, in the presence of silanol groups, the aluminumconcentration being maintained at less than 0.3 mol/l, the Al/Si molarratio being maintained between 1 and 3.6 and the alkali/Al molar ratiobeing maintained between 2.3 and 3;

b) stirring the mixture resulting from step a) at ambient temperature inthe presence of silanol groups long enough to form the aluminosilicatepolymer; and

c) eliminating the byproducts formed during steps a) and b) from thereaction medium.

According to one embodiment, the unmodified mixed aluminum and siliconprecursor can be formed in situ by mixing in aqueous medium (i) onecompound selected from the group consisting of aluminum salts, aluminumalkoxides and aluminum halogenoalkoxides and (ii) at least one compoundselected from the group consisting of unmodified silicon alkoxides andchloroalkoxides. The alkoxide radical of the unmodified aluminumcompound or silicon compound preferably contains 1 to 5 carbon atoms,such as methoxide, ethoxide, n-propoxide, or i-propoxide.

Preferably, an aluminum salt, such as a halide (e.g. chloride orbromide), a perhalogenate, a sulfate, a nitrate, a phosphate or acarboxylate, and at least one unmodified silicon alkoxide, such astetramethyl or tetraethyl orthosilicate is used.

A single unmodified silicon alkoxide or a mixture of unmodified siliconalkoxides, or a single unmodified silicon chloroalkoxide or a mixture ofunmodified silicon chloroalkoxides, or a mixture of unmodified siliconalkoxides and chloroalkoxides can be used.

Preferably, an aluminum halide, such as chloride, and an unmodifiedsilicon alkoxide is used. In practice, the mixture is made at ambienttemperature between 15° C. and 35° C., preferably between 20° C. and 25°C., by adding the silicon alkoxide, pure or diluted in a co-solvent suchas an alcohol, to the aluminum salt in aqueous solution, with stirring,until a clear homogeneous mixture is obtained. An unmodified mixedaluminum and silicon precursor is thus obtained. The stirring timevaries from 10 to 180 minutes, and is preferably 120 minutes.

According to step a) of the method for preparing the aluminosilicatepolymer useful in the invention, the precursor or an unmodified mixedaluminum and silicon alkoxide is then put in contact with an aqueousalkali, the aluminum concentration being maintained at less than 0.3mol/l, the Al/Si molar ratio being maintained between 1 and 3.6, and thealkali/Al molar ratio being maintained between 2.3 and 3.Advantageously, the aluminum concentration is between 1.5×10⁻² and 0.3mol/l and even more preferably between 4.4×10⁻² and 0.3 mol/l.Preferably, the Al/Si molar ratio is between 1 and 2.

Preferably, an aqueous solution of sodium, potassium or lithiumhydroxide, diethylamine or triethylamine with a concentration between0.5 M and 3 M, and preferably 3 M is used. The alkali can also be in theform of an hydroalcoholic solution.

The alkali is added to the precursor or to the unmodified mixed aluminumand silicon alkoxide at a rate preferably between 50 and 650mmoles/hour.

The alkali in step a) is added in the presence of silanol groups. Thesegroups can be supplied by glass or silica (glass wool) particles orbeads, which have superficial hydroxy groups. When the volume of liquidto be treated is large, it maybe desirable to increase the quantity ofbeads. The diameter of the beads can be between 0.2 and 5 mm andpreferably between 1 and 3 mm. To simplify the implementation of themethod for preparing the aluminosilicate polymer useful in the presentinvention, the preparation of the mixed aluminum and silicon precursorcan also be performed in the presence of silanol groups, for example bycirculating the mixture in a bed of glass beads.

After the addition of the alkali, step b) of the method for preparingthe aluminosilicate polymer useful in the present invention consists instirring the mixture resulting from step a) at ambient temperature inthe presence of silanol groups long enough to form the saidaluminosilicate polymer.

Then, step c) of the method for preparing the aluminosilicate polymeruseful in the present invention consists in eliminating from thereaction medium the byproducts formed during steps a) and b), such asthe residual ions coming essentially from the alkali used in step a).The residual ions can be eliminated by washing, by successivesedimentation or by diafiltration. The aluminosilicate polymer materialresulting from step c) can then be concentrated by centrifugation ornanofiltration.

In a first embodiment of the method for preparing the aluminosilicatepolymer useful in the present invention, during step a) a quantity ofalkali is added in order to obtain an alkali/Al molar ratio of about2.3. In this case the pH is maintained between 4 and 5, and preferablybetween 4.2 and 4.3. Then step b) as described above is applied. Thealuminosilicate polymer useful in the present invention is thus obtainedin dispersion form. Step c) to eliminate the residual ions can then beperformed by diafiltration, followed by nanofiltration concentration.

In a second embodiment of the method for preparing the aluminosilicatepolymer useful in the present invention, during step a) a quantity ofalkali is added in order to obtain an alkali/Al molar ratio of about 3.Then step b) as described above is applied. The aluminosilicate polymeruseful in the present invention is thus obtained in suspension form.Step c) to eliminate the residual ions can then be performed bydiafiltration, followed by nanofiltration concentration, thealuminosilicate polymer having been previously redispersed by addingacid, such as hydrochloric or acetic acid or a mixture thereof.

In a third embodiment, the method for preparing the aluminosilicatepolymer useful in the present invention comprises an additional step d),after step b) and before step c). Said step d) consists in adding in afew minutes an additional quantity of aqueous alkali to reach analkali/Al molar ratio of 3 if this ratio had not already been reachedduring step a). The aluminosilicate polymer useful in the presentinvention is thus obtained in suspension form. Step c) to eliminate theresidual ions can then be performed by diafiltration, followed bynanofiltration concentration, the aluminosilicate polymer having beenpreviously redispersed by adding hydrochloric acid. Step c) can also beperformed by washing with osmosed water by successive sedimentations,followed by centrifugation concentration.

The aluminosilicate polymer useful in the present invention resultingfrom step c) followed by concentration has physical gel form. The Al/Simolar ratio is between 1 and 3.6. Subsequent lyophilization enables thealuminosilicate polymer useful in the present invention to be obtainedas a powder. Such an aluminosilicate polymer can be characterized inthat its Raman spectrum comprises in spectral region 200-600 cm³¹ ¹ awide band at 250±6 cm⁻¹, a wide intense band at 359±6 cm⁻¹, a shoulderat 407±7 cm⁻¹, and a wide band at 501±6 cm⁻¹, the Raman spectrum beingproduced for the aluminosilicate polymer resulting from step b) andbefore step c) and lyophilized.

In another embodiment, the method for preparing the aluminosilicatepolymer useful in the present invention comprises an additional step e),after step c), by which at least one chelating agent of aluminum isadded to the aluminosilicate polymer resulting from step c). Then themixture is stirred. Subsequent evacuation by vacuum enables thealuminosilicate polymer useful in the invention to be obtained in solidform.

Said chelating agent of aluminum can be selected from the groupconsisting of carboxylic acids, phosphonic acids, sulfonic acids,difunctional acids, their ester and anhydride components and aminoacids. Preferably, the chelating agent of aluminum is selected from thegroup consisting of HCOOH, R₁COOH wherein R₁ is selected from the groupconsisting of CH₃(CH₂)_(n), n being between to 0 and 12, CF₃, C₆H₅,(C₆H₅)₂, substituted aromatic rings as in salicylic acid, C₄H₄S;R₂PO(OH)₂ wherein R₂ is selected from the group consisting of CH₃, C₆H₅;R₃SO₃H wherein R₃ is CH₃(CH₂)_(n), n being between to 0 and 5;HOOC(CH₂)_(n)COOH, n=0-8; aromatic difunctional acids as phtalic acid;HOOC(CH₂)_(n)PO(OH)₂, n=2, 4; hydroxy aliphatic acids;HOOC(CH₂OH)_(n)COOH, n=1-2; CH₃CH(NH₂)COOH. Preferably, the chelatingagent is acetic acid.

The useful solvent of chelating agent of aluminum is generally water butanother solvent miscible to water can be used in order to solubilize thechelating agent before its adding to the aluminosilicate polymerresulting from step c).

Step e) can be applied directly on the aluminosilicate polymer resultingfrom step c) to prepare a aluminosilicate polymer resulting from step e)or when a coating composition for the preparation of the ink-receivinglayer is prepared by using a aluminosilicate polymer resulting from stepc).

Step e) can comprise a first adding of acetic acid and a followingadding of another different chelating agent of aluminum. This method isparticularly useful to help the chelation when the chelating agentcomprises large bulky groups.

The amount of chelating agent of aluminum in the ink-receiving layercorresponds to a molar ratio between the chelating functions of thechelating agent and aluminum of the aluminosilicate polymer, whereinthis molar ratio is less than 1. Preferably, the molar ratio is greaterthan 0.1 and less than 1. The introduction of a chelating agent ofaluminum allows to modify the surface of the aluminosilicate polymer byforming a chelate compound. The functional group of the chelating agentallows to increase the affinity of the aluminosilicate polymer with themedium in which it is used.

The Raman spectrum of the aluminosilicate polymer material resultingfrom step e) comprises the same bands as the aluminosilicate polymermaterial resulting from step b), as well as bands corresponding to thechelating agent in its chelate form. The aluminosilicate polymer usefulin the present invention resulting from step e) has physical gel form.The Al/Si molar ratio is between 1 and 3.6.

The ink-receiving layer comprises from 5 to 95 percent by weight ofaluminosilicate polymer compared with the total weight of the dry stateink-receiving layer.

The present invention also relates to the composition intended to becoated on the support to constitute the ink-receiving layer of therecording element described above. To produce this composition, thehydrosoluble binder is diluted in water to adjust its viscosity andfacilitate its coating. The composition then has the form of an aqueoussolution or a dispersion containing all the necessary components. Whenthe aluminosilicate polymer as obtained above is used for preparing thecomposition as a powder, this powder must be very fine.

The composition can also comprise a surfactant to improve its coatingproperties. The composition can be coated on the support according toany appropriate coating method, such as blade, knife or curtain coating.The composition is applied with a thickness between approximately 100 μmand 200 μm in the wet state. The composition forming the ink-receivinglayer can be applied to both sides of the support. It is also possibleto provide an antistatic or anti-winding layer on the back of thesupport coated with the ink-receiving layer.

The ink jet recording element according to the invention can comprise,besides the ink-receiving layer described above, other layers havinganother function, arranged above or below said ink-receiving layer. Theink-receiving layer as well as the other layers can comprise all theother additives known to those skilled in the art to improve theproperties of the resulting image, such as UV ray absorbers, opticalbrightening agents, antioxidants, plasticizers, etc.

The ink-receiving layer useful in the present invention has a thicknessgenerally between 5 μm and 50 μm in the dry state. The ink jet recordingelement comprising such an ink-receiving layer has improved dye keepingproperties in time as well as gloss. It can be used for any type ofinkjet printer as well as for all the inks developed for thistechnology.

The following examples illustrate the present invention without howeverlimiting the scope.

1) Preparation of Various Aluminosilicates

EXAMPLE 1

An aluminosilicate polymer in hollow sphere form was prepared accordingto the method described in Patent U.S. Pat. No. 6,254,845.

Sodium orthosilicate was dissolved in purified water to obtain 50 ml ofan aqueous solution at 0.1 mol/l. Separately, aluminum chloride wasdissolved in purified water to obtain 67.15 ml of an aqueous solution at0.1 mol/l. The aluminum chloride solution was mixed at high speed withthe aqueous solution of sodium orthosilicate. At this stage, thealuminum concentration was 5.7×10⁻² mol/l. The Al/Si molar ratio was1.34. The mixture was stirred for one hour at ambient temperature. Asuspension was obtained that was filtered using a membrane filter toeliminate byproducts such as sodium chloride. The retentate that adheredto the filter was recovered, and 120 ml of purified water was added toit. The mixture was dispersed using ultrasound for one hour and thenwarmed for five days at 80° C., washed with purified water, and dried innormal conditions of temperature and pressure, and then lyophilized. Analuminosilicate polymer was obtained in hollow spherical particle form.This polymer was identified by its Raman signature or spectrumrepresented by FIG. 1.

In all the examples described, a Raman Bruker RFS 100 spectrometer(laser exciting wavelength, 1064 nm, power 800 mW and 512 scans) wasused to obtain the Raman spectra The spectra were acquired in reflectionmode (180°) using a lens with semi-cylindrical mirror. Samples wereanalyzed in solid form (obtained by lyophilization) without specialpreparation. The Raman spectrum instead of infrared spectrum waspreferred, because the materials used in the present invention werewater rich and the infrared spectrum of the material was then masked bythe water. This problem did not appear with the Raman spectratechnology. Materials that have the same Raman signature belong to thesame family.

EXAMPLE 2

4.53 moles AlCl₃, 6H₂O, then 2.52 moles tetraethyl orthosilicate wereadded to 100 l osmosed water. This mixture was stirred and circulatedsimultaneously through a bed formed of 1-kg glass beads 2-mm diameterusing a pump with 8-1/min output. The operation to prepare theunmodified mixed aluminum and silicon precursor took 60 minutes. Then,according to step a) of the method for preparing the aluminosilicatepolymer used in the present invention, 10.5 moles NaOH 3M were added tothe precursor in two hours. The reaction medium clouded. According tostep b) of the preparation method, the mixture was stirred for 18 hours.The medium became clear. The circulation was stopped in the glass beadbed. Then, according to step d) of the preparation method, 3.09 molesNaOH 3M were added in ten minutes. Aluminum concentration was 4.4×10⁻²mol/l, Al/Si molar ratio 1.8 and alkali/Al ratio 3. The aluminosilicatepolymer useful in the present invention was thus obtained as asuspension. FIG. 2 represents the Raman spectrum of this polymer thatwas lyophilized to obtain its Raman signature. Step c) of thepreparation method consisted in leaving the polymer suspension to settlefor 24 hours, then in discarding the supernatant to recover thesediment. This sediment was washed with osmosed water by successivesedimentations to obtain a sodium level in the supernatant less than 10ppm. Then the sediment was centrifuged to obtain a gel with about 4% byweight of aluminosilicate polymer according to the invention. Theresulting gel was lyophilized (20 mT, −50° C.) to obtain a solid ofconstant mass. The aluminosilicate polymer useful in the presentinvention was then obtained as a powder. For its use in the compositionthat is going to constitute the ink-receiving layer, the powder can beredispersed by adding water and acid, such as hydrochloric or aceticacid, and with mechanical stirring.

EXAMPLE 3

100 l of osmosed water were poured into a plastic (polypropylene)reactor. 4.53 moles AlCl₃, 6H₂O, then 2.52 moles tetraethylorthosilicate were added. This mixture was stirred and circulatedsimultaneously through a bed formed of 1-kg glass beads 2-mm diameterusing a pump with 8-1/min output. The operation to prepare theunmodified mixed aluminum and silicon precursor took 90 minutes. Then,according to step a) of the preparation method, 10.5 moles NaOH 3M wereadded to the contents of the reactor in two hours. Aluminumconcentration was 4.4×10^(—2) mol/l, Al/Si molar ratio 1.8 and alkali/Alratio 2.31. The reaction medium clouded. According to step b) of thepreparation method, the mixture was stirred for 48 hours. The mediumbecame clear. The circulation was stopped in the glass bead bed. Thealuminosilicate polymer used in the present invention was thus obtainedas a dispersion. FIG. 3 represents the Raman spectrum of this polymerthat was lyophilized to obtain its Raman signature. Step c) of thepreparation method consisted in performing preconcentration by a factorof 3 by nanofiltration, then diafiltration using a Filmtec NF 2540nanofiltration membrane (surface area 6 m²) to eliminate the sodiumsalts to obtain an Al/Na rate greater than 100. The retentate resultingfrom the diafiltration by nanofiltration was concentrated to obtain agel with about 20 percent by weight of aluminosilicate polymer used inthe present invention.

EXAMPLE 4

20 moles AlCl₃, 6H₂O, then 4.5 kg glass beads 2-mm diameter, then 11.1moles tetraethyl orthosilicate were added to 100 1 osmosed water. Thismixture was stirred vigorously. The operation to prepare the unmodifiedmixed aluminum and silicon precursor took 30 minutes to obtain a clearhomogeneous medium. Then, according to step a) of the preparationmethod, 60 moles NaOH dissolved in 100 liters of osmosed water wereadded to the reaction medium, in 30 minutes. The reaction mediumclouded. Aluminum concentration was 0.1 mol/l, Al/Si molar ratio 1.8 andalkali/Al ratio 3. According to step b) of the preparation method, themixture was stirred for 15 minutes. The aluminosilicate polymer used inthe present invention was thus obtained as a suspension. Step c) of thepreparation method consisted in adding 930 g HCl 37 percent firstdiluted 10 times and stirring for 150 minutes to obtain a dispersion ofthe aluminosilicate polymer. The dispersion was then diafiltrated usinga Filmtec NF 2540 nanofiltration membrane (surface area 6 m²) toeliminate the sodium salts to achieve an Al/Na ratio greater than 100.The retentate resulting from the diafiltration by nanofiltration wasconcentrated to obtain a gel with about 20 percent by weight ofaluminosilicate polymer used in the present invention.

2) Preparation of Coating Compositions Constituting an Ink-ReceivingLayer Coated on a Support

As hydrosoluble binder of polyvinylic alcohol (Gohsenol™ GH23 marketedby Nippon Gohsei) diluted 9 percent in osmosed water and as receivingagent the aluminosilicate polymers prepared according to examples 1 to 4were used, as well as an aqueous dispersion of pyrogenated alumina(CAB-O-SPERSE® PG003 marketed by Cabot), an aqueous solution ofcolloidal silica (Ludox™ TMA marketed by Grace Corporation) and boehmite(Disperal™ HP 14/2 marketed by Sasol).

All the compositions resulted from mixing:

15.22 g water

3 g receiving agent (dry matter)

4 g polyvinylic alcohol.

When the receiving agent has powder form, the particles must first becrushed finely.

3) Preparation of Ink Jet Recording Elements

To do this, a Resin Coated Paper type support was placed on a coatingmachine, first coated with a very thin gelatin layer, and held on thecoating machine by vacuum. This support was coated with a composition asprepared according to paragraph 2 using a spiral filmograph 125 μmthick. Then, it was left to dry overnight at ambient air temperature(21° C.).

The resulting recording elements correspond to the examples shown inTable I below giving the receiving agent used in the ink-receivinglayer: TABLE I Recording element Receiving agent in the ink-receivinglayer Ex 5 (comp.) Aluminosilicate prepared according to Example 1 Ex 6(inv.) Aluminosilicate prepared according to Example 2 Ex 7 (inv.)Aluminosilicate prepared according to Example 3 Ex 8 (inv.)Aluminosilicate prepared according to Example 4 Ex 9 (comp.)CAB-O-SPERSE ® PG003 Ex 10 (comp.) Ludox ™ TMA Ex 11 (comp.) Boehmite(Disperal ™ HP 14/2)4) Evaluation of Dye Keeping Properties in Time

To evaluate the dye keeping properties in time, a dye fading test byexposure to ozone was performed for each resulting recording element. Todo this, targets comprising four colors (black, yellow, cyan andmagenta) were printed on each recording element using a Lexmark KODAKPPM 200 printer and related ink. The targets were analyzed using aVannier-Photelec densitometer that measures the density of the variouscolors. Then the recording elements were placed to the dark in a roomwith controlled ozone atmosphere (60 ppb) for three weeks. Each week,any degradation of the color density was monitored using thedensitometer. If density losses were less than 10 percent, for all thecolors, it was considered that the recording element enablesparticularly stable printing to be obtained.

FIG. 4 represents the percentage of density loss observed for theoriginal density 0.5 for the four colors of the targets after one weekfor examples 6 and 8, 9, 10. Letters K, C, M and Y represent the colorsblack, cyan, magenta and yellow respectively.

It may be seen that ink jet recording elements according to theinvention have good dye keeping properties in time compared withrecording elements containing other inorganic receiving agents availableon the market. In particular, the color magenta is much more degradedfor the comparative examples than for recording elements according tothe invention.

FIGS. 5 to 9 represent the percentage of density loss observed accordingto the original densities for the four colors of the targets after threeweeks for examples 5, 6, 7, 9 and 11 respectively. Once again, thefigures clearly demonstrate that the recording elements according to theinvention (Ex 6 and 7 corresponding to FIGS. 6 and 7) have very good dyekeeping properties compared with the recording elements containinginorganic receiving agents available on the market (Ex 5, 9 and 11) andare approximately stable for all the colors. On the other hand, up to90-95 percent of density loss for the color magenta and up to 85-90percent of density loss for the color cyan for the comparative Examples5 and 11 corresponding to FIGS. 5 and 9 can be seen.

The tests were repeated using an Epson 670 printer and the related Epsonink for the recording elements of examples 5 and 6. FIGS. 10 and 11represent the percentage of density loss observed according to theoriginal densities for the four colors of the target after three weekfor said examples 5 and 6 respectively. The colors of the recordingelement according to the invention (FIG. 11) are approximately stablewhile the colors cyan and magenta of the recording element of thecomparative Example 5 lose between 30 and 40 percent density.

5) Evaluation of the Gloss

Gloss was measured for various resulting recording elements using aPicogloss 560 apparatus (60° geometry) marketed by Erichsen.

The results are given below in Table II. TABLE II Gloss Recordingelement (percent) Ex 5 (comp.) 2 Ex 7 (inv.) 55 Ex 11 (comp.) 45The results of Table II show that the recording elements according tothe present invention show a good gloss, which is wanted to reproducethe gloss of photographs developed by a conventional silver process.6) Examples 12-16 of Aluminosilicate Polymers

EXAMPLE 12

The procedure of example 2 was repeated, except that step c) of themethod for preparing the aluminosilicate polymer used in the inventionconsisted in leaving the resulting polymer suspension to settle for 24hours, then in discarding the supernatant to recover the sediment. Then166 g HCl 37%, previously diluted 10 times, were added to the sedimentto obtain a dispersion of the aluminosilicate polymer. The dispersionwas then diafiltrated using a Filmtec NF 2540 nanofiltration membrane(surface area 6 m²) to eliminate the sodium salts to achieve an Al/Naratio greater than 100. Then the retentate resulting from thediafiltration by nanofiltration was concentrated to obtain a gel withabout 20% by weight of aluminosilicate polymer useful in the invention.

EXAMPLE 13

100 g of gel of aluminosilicate polymer obtained in Example 12 (Alamount=1.54 g, 57 mmol, measured by inductively coupled plasma atomicemission spectroscopy, ICP) was diluted with 100 g of osmosed water.Glacial acetic acid (1.7 g, 28.3 mmol) was added to the gel. The mixturewas stirred during 2 days. The excess of water and the unreacted aceticacid were removed by evacuation under vacuum at 35° C. A white powderwas obtained. The Raman spectrum of this aluminosilicate polymermaterial comprises the bands of the aluminosilicate polymer obtained inExample 2, as well as the bands corresponding to the chelating agent inits acetate form.

EXAMPLE 14

100 g of gel of aluminosilicate polymer obtained in Example 12 (Alamount=1.54 g, 57 mmol) was diluted with 100 g of osmosed water.Propionic acid (2.0 g, 27.7 mmol) was added to the gel. The mixture wasstirred during 2 days. The excess of water and the unreacted acetic acidwere removed by evacuation under vacuum at 35° C. A white powder wasobtained. The Raman spectrum of this aluminosilicate polymer materialcomprises the bands of the aluminosilicate polymer obtained in Example2, as well as the bands corresponding to the chelating agent in itspropionate form.

EXAMPLE 15

Methyl phosphonic acid powder (1.7 g, 10.4 mmol) was solubilized inethanol (10 ml). 40 g of gel of aluminosilicate polymer (Al amount=0.950g, 35 mmol) obtained in Example 12 diluted with 20 g of osmosed waterwere added to the alcoholic solution of methyl phosphonic acid. Themixture was stirred during 4 days. The excess of ethanol was removed byevacuation under vacuum at 35° C. A white powder was obtained.

EXAMPLE 16

20 g of gel of aluminosilicate polymer (Al amount=0.8 g, 29 mmol)obtained in Example 12 was diluted with 20 g of osmosed water. Methylsulfonic acid (1.6 g, 16.6 mmol) was added to the gel. The mixture wasstirred during 4 days. The excess of water was removed by evacuationunder vacuum at 35° C. A white powder was obtained.

7) Preparation of Coating Compositions Constituting an Ink-ReceivingLayer Coated on a Support

As hydrosoluble binder of polyvinylic alcohol (Gohsenol™ GH23 marketedby Nippon Gohsei) diluted 9 percent in osmosed water and as receivingagent the aluminosilicate polymers prepared according to examples 13 to16 were used.

All the compositions resulted from mixing:

10.1 g water

2 g receiving agent (dry matter)

2.7 g polyvinylic alcohol.

When the receiving agent has powder form, the particles must first becrushed finely. The mixtures were sheared overnight.

8) Preparation of Ink Jet Recording Elements

A Resin Coated Paper type support was placed on a coating machine, firstcoated with a very thin gelatin layer, and held on the coating machineby vacuum. This support was coated with a composition as preparedaccording to paragraph 7 using a blade. The wet thickness was 125 μm.Then, it was left to dry 3 hours at ambient air temperature (21° C.).

The resulting recording elements correspond to the examples shown inTable III below giving the receiving agent used in the ink-receivinglayer: TABLE III Recording element Receiving agent in the ink-receivinglayer Ex 17 (inv.) Aluminosilicate prepared according to Example 13 Ex18 (inv.) Aluninosilicate prepared according to Example 14 Ex 19 (inv.)Aluminosilicate prepared according to Example 15 Ex 20 (inv.)Aluminosilicate prepared according to Example 169) Evaluation of Dye Keeping Properties in Time

The evaluation of dye keeping properties was made as in paragraph 4.

FIGS. 12 and 13 represent the percentage of density loss observed forthe original density 0.5 for the four colors of the target for each weekfor Example 17 printed using the Lexmark Kodak PPM200 printer andrelated ink and an Epson 670 printer and related Epson ink respectively.Letter C, M, Y and K represent the colors cyan, magenta, yellow andblack respectively.

FIGS. 14 and 15 represent the percentage of density loss observed forthe original density 0.5 for the four colors of the target for each weekfor Example 18 printed using the Lexmark Kodak PPM200 printer andrelated ink and an Epson 670 printer and related Epson ink respectively.

FIGS. 16 and 17 represent the percentage of density loss observed forthe maximum density for the four colors of the target for each week forExample 19 printed using the Lexmark Kodak PPM200 printer and relatedink and an Epson 670 printer and related Epson ink respectively.

FIGS. 18 and 19 represent the percentage of density loss observed forthe maximum density for the four colors of the target for each week forExample 20 printed using the Lexmark Kodak PPM200 printer and relatedink and an Epson 890 printer and related Epson ink respectively.

The figures clearly demonstrate that the recording elements according tothe invention have very good dye keeping properties.

10) Evaluation of the Gloss

Gloss was measured for resulting recording elements of Examples 17-19using a Picogloss 560 apparatus (60° geometry) marketed by Erichsen.

The results are given below in Table IV. TABLE IV Gloss Recordingelement (percent) Ex 17 (inv.) 30 Ex 18 (inv.) 50 Ex 19 (inv.) 30

The results of Table IV show that the recording elements according tothe present invention show a good gloss, which is wanted to reproducethe gloss of photographs developed by a conventional silver process.

1. An ink jet recording element comprising a support and at least oneink-receiving layer, wherein said ink-receiving layer comprises at leastone hydrosoluble binder and at least one aluminosilicate polymerobtainable by a preparation method that comprises the following steps:a) treating a mixed aluminum and silicon alkoxide only comprisinghydrolyzable functions, or a mixed aluminum and silicon precursorresulting from the hydrolysis of a mixture of aluminum compounds andsilicon compounds only comprising hydrolyzable functions, with anaqueous alkali, in the presence of silanol groups, the aluminumconcentration being maintained at less than 0.3 mol/l, the Al/Si molarratio being maintained between 1 and 3.6 and the alkali/Al molar ratiobeing maintained between 2.3 and 3; b) stirring the mixture resultingfrom step a) at ambient temperature in the presence of silanol groupslong enough to form the aluminosilicate polymer; and c) eliminating thebyproducts formed during steps a) and b) from the reaction medium. 2.The recording element according to claim 1, wherein the alkali of stepa) to prepare the aluminosilicate polymer is selected from the groupconsisting of sodium, potassium, and lithium hydroxide, diethylamine,and triethylamine.
 3. The recording element according to claim 1,wherein the silanol groups used to prepare the aluminosilicate polymerare supplied in silica or glass bead form.
 4. The recording elementaccording to claim 1, wherein the aluminum concentration used to preparethe aluminosilicate polymer is maintained between 1.5×10⁻² and 0.3mol/l.
 5. The recording element according to claim 1, wherein thealuminum concentration used to prepare the aluminosilicate polymer ismaintained between 4.4×10⁻² and 0.3 mol/l.
 6. The recording elementaccording to claim 1, wherein said alkali/Al molar ratio to prepare thealuminosilicate polymer is about 2.3.
 7. The recording element accordingto claim 1, wherein said alkali/Al molar ratio to prepare thealuminosilicate polymer is about
 3. 8. The recording element accordingto claim 1, wherein the method for preparing the aluminosilicate polymercomprises, after step b) and before step c), a step d), by which alkaliis added in order to reach an alkali/Al molar ratio of 3 if this ratiohas not already been reached in step a).
 9. The recording elementaccording to claim 1, wherein the mixed aluminum and silicon precursorresulting from hydrolysis of a mixture of aluminum compounds and siliconcompounds only having hydrolyzable functions is a product resulting fromthe mixture in an aqueous medium (i) of a compound selected from thegroup consisting of aluminum salts, aluminum alkoxides and aluminumhalogenoalkoxides and (ii) at least one compound selected from the groupconsisting of silicon alkoxides and chloroalkoxides only havinghydrolyzable functions.
 10. The recording element according to claim 9,wherein said mixed aluminum and silicon precursor is the productresulting from the mixture (i) of an aluminum halide and (ii) a siliconalkoxide only having hydrolyzable functions.
 11. The recording elementaccording to claim 10, wherein said silicon alkoxide only havinghydrolyzable functions is tetramethyl orthosilicate or tetraethylorthosilicate.
 12. The recording element according to claim 1, whereinthe method for preparing the aluminosilicate polymer comprises, afterstep c), a step e), by which at least one chelating agent of aluminum isadded to the aluminosilicate polymer resulting from step c), wherein theamount of the chelating agent in the ink-receiving layer corresponds toa molar ratio between the chelating functions of the chelating agent andaluminum of the aluminosilicate polymer, and wherein this molar ratio isless than
 1. 13. The recording element according to claim 12, whereinstep e) is applied directly on the aluminosilicate polymer resultingfrom step c) to prepare a aluminosilicate polymer resulting from step e)or when a coating composition for the preparation of the ink-receivinglayer is prepared by using a aluminosilicate polymer resulting from stepc).
 14. The recording element according to claim 12, wherein saidchelating agent of aluminum is selected from the group consisting ofcarboxylic acids, phosphonic acids, sulfonic acids, difunctional acids,their ester and anhydride components and amino acids.
 15. The recordingelement according to claim 14, wherein said chelating agent of aluminumis selected from the group consisting of HCOOH, R₁COOH wherein R, isselected from the group consisting of CH₃(CH₂)_(n), n being between to 0and 12, CF₃, C₆H₅, (C₆H₅)₂, substituted aromatic rings, C₄H₄S; R₂PO(OH)₂wherein R₂ is selected from the group consisting of CH₃, C₆H₅; R₃SO₃Hwherein R₃ is CH₃(CH₂)_(n), n being between to 0 and 5;HOOC(CH₂)_(n)COOH, n=0-8; aromatic difunctional acids;HOOC(CH₂)_(n)PO(OH)₂, n=2, 4; hydroxy aliphatic acids;HOOC(CH₂OH)_(n)COOH, n=1-2; CH₃CH(NH₂)COOH.
 16. The recording elementaccording to claim 12, wherein step e) comprises a first adding ofacetic acid and a following adding of another different chelating agentof aluminum.
 17. The recording element according to claim 1, whereinsaid ink-receiving layer comprises between 5 and 95 percent by weight ofaluminosilicate polymer compared with the total weight of the dryink-receiving layer.
 18. The recording element according to claim 1,wherein the hydrophilic binder is gelatin or polyvinyl alcohol.
 19. Acoating composition for the preparation of ink-receiving layers for theink jet recording element according to claim 1.